Process of producing a mineral oil



Patented Nov. 12, 1935 UNITED STATES PATENT OFFICE PROCESS OF PRODUCINGA MINERAL OIL SUBSTITUTE PAINT VEHICLE Giovanni Fiore, New York, N. Y.

No Drawing. Application July 10, 1934, Serial No. 734,511

2 Claims.

stitute for linseed oil and other similar oils, ca-

pable of oxidizing and drying, while its selling price may be less thana fourth of that of linseed oil. Up to comparatively recent timesmineral oils could not be used like certain Vegetable oils or organicfats as vehicles for pigments or bases for lacquers, having no dryingqualities, and even the addition of driers or oxidizing agents to themdid not remedy this deficiency. The numerous attempts to convert variousforms or derivatives of such mineral oils into oxidizable drying oilshave been only partly successful, and the difficulties become obvious ifwe investigate the phenomena taking place when a paint or a lacquer witha suitable drying base solidifies. Assuming, for example, a pigmentcarrier like boiled linseed oil or castor oil (the latter being used incoating compositions for artificial leather), the drying process is notaccomplished by the loss and evaporation of water, but by the oxidationof liquid fatty acids (oleic, linolic, linolenic, isolinolenic) or solidacids (palmitic and stearic) in linseed oil or other vegetable oils.These acids, being exposed to the air, tend to absorb oxygen, and formsolid oxides. Certain glycerides present in the mineral oils promotethis solidifying process by esterifying the free aldehyde-fatty acidspresent and act therefore as exciters of oxidation. The glycerides oflinolic, linolenic, isolinolenic or oleic acids enter completely intothis oxidizing process while the glycerides of other acids act in asimilar way. The final products of the oxidation of linseed oil,commonly called Linoxyn, are probably a mixture of solid oxides oflinolenic and isolinolenic acids, oxidized glycerides and a trace ofglycerine.

In mineral oils, however, these fatty acids are absent, and thereforethey exhibit no drying or oxidizing power.

As far as these mineral oils and their related asphaltic compounds areconcerned, one usually distinguishes two main classes, one class whichcomprises saturated hydrocarbons, having a paraffin basis (petroleumoils, found east of the Mississippi River, Pennsylvania, etc., are ofthis class) and one class, having an asphaltic base and consistinglargely of unsaturated hydrocarbons or olefins (Texas, Gulf orCalifornia oils). While both kinds have in themselves no dryingqualities, experiments tooxidize mineral oils of 5 the second class orat least their derivatives have been partly successful, while thelighter and more liquid oils of the first class-which contained more orless paraflins-have proven more recalcitrant to any oxidizing treatment.thermore, rather high temperatures seemed necessary but at elevatedtemperatures considerable darkening andeven decomposition takes place.The broader object of the present invention is to devise a methodwhereby mineral oils with a 15 paraflin basis can be just assuccessfully converted into oxidizable oils at a comparatively lowtemperature (100 C.) and within a short time, as mineral oils, in whichthe parafiins are missing,

or from which they have been artificially removed, 20

and both kinds in the same way and same period of time.

The leading principle of my invention is that I introduce the missingelements, the fatty acids,

indirectly by means of a suitable vehicle into the 5 mineral oil. Thisis the first step, but in itself would not be sufi'icient even if acatalyst were added, to induce complete oxidation. The second concurrentprinciple of my method is that instead of simple oxygen I use the morepotent form ozone (O3) and submit the mineral oil containing the fattyacids to a current of ozone.

But what in my estimation is the most potent agent to complete theoxidizing process, once the favorable preliminary conditions are given,as

above described, is the addition of alcohol and nitric acid incombination. Alcohol itself has a strong power of developing oxygen, butits combination with nitric acid or derivatives of the latter increases,as I found, this power in a sur- 40 of a normally unoxidizable mineraloil may be converted into an oxidizable oil.

A further object is to convert a normally un-' oxidizable residue ofcrude oil, from which the paraifins have been removed by fractionaldistillation, into an oxidized or oxidizable form.

Filr- 10 A further object is to devise a method whereby theresidue of anatural mineral oil wherefrom certain valuable constituents have beenremoved by the so-called cracking process, may be converted into avaluable product in the form of an oxidizable mineral oil.

Another object is to' devise a method whereby mineral oil of anyconstituency, whether in the natural state, or after undergoingfractional distillation, may be converted into an oxidizable oil withoutthe necessity of previously removing therefrom any constituents,generally considered recalcitrant to an oxidizing process, likeparaifins,

etc.

A further object of my invention. is to manufacture from crude oil ofany, description, a

non-expensive substitute for linseed oil.

A further object of my invention is to manufacture from crude'oil or itsfractional deriva tives an oxidizable oil which can be usedadvantageously as a substitute for any vegetable oils commonly used asvehicles for pigments.

Another more specific object of my invention is to provide an admixture,which, when blended with crude oil or any of its fractional derivatives,and combined with them in a certain definite way, will impart to saidoil or its derivatives the quality of spontaneous oxidization.

Another object is to provide such admixture in the form of a vegetableoil which will contain the active ingredients, i. e., the fatty acids,in a certain suitable definite proportion.

A further object of my invention is to initiate the oxidation of saidfatty acids by the introduction of oxygeniin a specially potent form.

A similar object is to initiate the oxidation of said mixture of crudeoils and fatty acids by the introduction of oxygen in the form of ozone.

A similar object is to initiate the oxidation of said fatty acids byozonizing the air brought into intimate contact with them during theirfirst stage of oxidation. 7

A further object of my invention is to provide certain admixtures forthe crude oil or its derivatives, while undergoing the initial steps ofoxidation, which will serve as powerful stimulants in this oxidationprocess.'

' method is better understood and the steps are explained in detail. 7

The disclosure made the basis of exemplifying the present inventiveconcept suggests a practical embodiment thereof, but the invention isnot to be. restricted to the exact details of this disclosure nor to theexact quantities set forth in the formulas which are to be taken ratheras i1lustrative than as restrictive.

Itislalso to be understood that the various steps of the processdisclosed may be separately applicable despite their cooperation hereinshown, and that also all possible chemical equivalents instead of themedia enumerated would 'B.Preparation and ozonization come within thelegitimate scope of the invention.

I shall now describe my process in detail. For the sake of a betterunderstanding and distinction of principal steps, my'process may be (11-5 residue of the crude oil, the addition of certain metal oxide driersto the crude oil, besides a protective colloid to prevent precipitation,and the intimate combination of these ingredients by heating at lowtemperature. a 15 B comprises the heating of the crude oil or whateverfractional part or'residue of it is to be treated, the incorporation ofthe admixture prepared according to A into it, and the treatment of thiscompound mixture by ozone. 20 C comprises the treatment of the ozonizedcompound by a mixture of alcohol and nitric acid, the addition of avolatiledrier and the ageing of the finished product.

A.Preparationo,f the admixture 25 Although there is apparently a greatchoice of oxidizable vegetable oils" which contain fatty acids in moreor lesssuitable proportions and which therefore could be usedadvantageously to carry out my process, there are to be found among theavailable oils suchwhich also contain methyienic ether, and thisingredient I found to be especially helpful in oxidation. Thisingredient is, for example, to be found in Sesarnum '5 Indicum oil whichcontains its fatty acids also 7 in other respects in a proportion thatmight be taken as a model. -Such oil, if of best quality, willapproximately contain:

, Per cent 40 Oleic acid, CnH33COOH 17.50 Palmitic acid, C1sH3202 8Stearic acid, CH3(CH2)16CO2H 8 Linolic acid, C18H3202 30 Iso-linolenicacid, C13H3oO2 2'7 45 Methylenic ether, (CH3)2O 5 Glycerine, C3I-I5(OH-)3 4.5

Of this vegetableoil I take a quantity which would be equal to about 10%of the predeter: r mined total quantity of the finished'product. I heatthis oil to a temperature of about C. while I add to it certain driersin the form of metallic oxide; For example- V H Per cent Lead resinate(fusedor precipitated and dissolved in a volatile solvent or vegetable'oil) 5 Cobalt resinate 1 Manganese resinate i. 1 f

I reserve, however, the right to use other metallic 60 oxides which areusedas catalysts or driers instead, for instance, iron or molybdenumsalts, etc. In order to prevent precipitation or settling out of thesedriers, I may add. an equilibrator or protective colloid'to the mixtureand 65 recommend forinstance cadmium resinate, of which about 2% couldbeadded, Themixture is' to be kept heated moderately until theingredientsseem thoroughly absorbed. l a

of the main mixture Of the crude mineral oil or whatever oil residue isto be treated, about 52 per cent of the total finished product have tobe taken and slowly heated until about 100" C. are reached. Then theadmixture prepared in the first part A of the process is added to themineral oil. Connected by a valve and conduit with the container inwhich the crude oil is heated and combined with the vegetable oilingredient, is an ozone generator which can be of any ordinarycommercial make, electrically operated or otherwise. After the heatingof the oil compound has been maintained around 100 C. for about onehour, a current of nascent ozone is blown through it for approximatelyanother hour.

C.Intensified oxidation of alcohol andv nitric acid-ageing The lastphase of the process comprises the addition of an alcohol, such as woodor grain alcohol, diluted in nitric acid, to the mixture, and thequantity added should amount to about 16% of methylic or ethylic alcoholwith about 8% concentrated nitric acid in proportion to the total amountof finished product, as predetermined. Likewise, I add a volatile drier,such as spirits of turpentine in the dosage of about 5% of the total.The addition of turpentine, when introduced into the mineral oilpreviously treated by my process, produces an auto-ebulition lastingabout thirty minutes with an escape of gas in the form of a foamamounting in a volume to about 40 percent of the total compound. Suchgas when in contact with the atmosphere absorbs strongly oxygen whichthen is of course embodied into the compound by agitation. The mixturecools off spontaneously after about one hour. This well equilibratedcompound is to be left standing for several days without stirring, afterwhich period the finished product can be decanted and filtered throughcotton gauze or a similar filtering material. If the ageing period isprolonged, the drying qualities are still improved. Then the product isready for 'use or shipment. It may be used entirely in place of linseedoil.- The ingredients which in the course of the process enter into themixture total up as follows:

Per cent Crude oil (natural or residual) 52 Vegetable oil (fatty acids)l Cadmium resinate 2 Lead resinate 5 Cobalt resinate 1 Manganeseresinate 1 Alcohol (methyl or ethyl) 16 Nitric acid 8 Turpentine(volatile drier) 5 Total 100 The treatment with nitric acid or thedilution of the alcohol may be modified within a certain range. Bynumerous experiments I found that I could effect full oxidation of themineral oil when using nitric acid of 68% of concentration and in adosage of from 5 to 10%, diluted in alcohol provided in the dosage of to30%. I furthermore discovered that instead of nitric acid I could usenitrates in their original form or as a derivative, dissolved in alcoholor a similar suitable solvent, either used alone or in combination, togood advantage as far as the promotion of oxidation is concerned, and Itherefore claim the right to use nitrates and their derivatives insteadof nitric acid, whether they are adapted to develop the acid duringtreatment or not, for diluting the alcohol used and for the purposesindicated.

It behooves nowto consider'sorne of the reactions and transformationstaking place in the mixture, while under treatment, more in detail.

While the fatty acids of the liquid glycerines are unsaturatedhydrocarbons, the hydrocarbons 5 of the paraffin series or those in theasphaltic mineral oil are saturated and are therefore more or lessindilferent to the action of oxygen. However, they are renderedreceptive to it by the phenomenon of hydrogenation, which takes place 103 when fatty acids are introduced. These fatty acids, whether isolatedor in combination with other unsaturated fats, attack the double ortriple atomic carbon structure in the saturated hydrocarbons, and unitewith the hydro-gen atom, 15 and while becoming thus hydrogenatedconvertthe hydrocarbons thus attached into unsaturated acids. Linolic andlinolenic acids, for example, act this way and by taking up oxygen arethemselves transformed into resinous substances. Oleic acid deprives themineral oil of part of its hydrogen and is transformed thereby intosolid stearic acid. Even the saturated hydrocarbons of the aliphaticseries can be changed into oxidizable products by this hydrogenation.

A further characteristic of the fatty acids is that when they come intocontact with pure nitric acid or even with nitrates, they form atvarious temperatures crystallized stereo-isomers; for example, oleicacid is changed thereby into elaidic acid or elaidin, the elaidic esterof glycerine. These fatty acids therefore have the property to undergooxidation upon coming into contact with concentrated or diluted nitricacid.

Ozone as an oxidizing agent is much more energetic than simple oxygen,although it should be noted that only the third atom of each ozonemolecule plays the active part, while the rest is transformed into plainoxygen.

The strong-catalytic power of cobalt is fully realized at theaforementioned temperature of 100 C. and the unsaturated fatty acids ofthe liquid glycerines are changed into the saturated acids of solidglycerines, ultimately then the oleic, linoleic and iso-linolenic acidsare completely transformed into solid stearic acid.

This mineral oil, made oxidizable by the process described can be usedentirely like linseed or a similar vegetable oil and can be used as the60 carrier or base for innumerable anhydrous pigments; for example, zincoxide, zinc sulphide, lead sulphate or leaded zinc, barium sulphate,white lead, etc., also, if it is derived from more viscous mineral oils,as the base for printing and lithographic inks, stamping inks, etc.

Of the peculiar advantages of this o-xidizable mineral oil, whether usedalone as a varnish or as a pigment carrier, it may be mentioned thatpaints prepared with this vehicle dry and oxidize perfectly in from sixto eight hours, according to climatic conditions. These paints arelikewise weather-resistive, whether exposed to high or low temperatures.Under exposure to solar rays or rain they do not discolor or blacken.Their durability is by no means inferior, if not superior to ordinaryvegetable oil paints. The film they form remains durable, solid andflexible, so that it does not crack or plaster off. It is thus obviousthat all the listed objects of my invention are fulfilled in asatisfactory, economical and inexpensive way and a perfect cheapsubstitute for the expensive linseed and similar vegetable oils can bemanufactured from almost worthless resi dues of mineral oils andasphalts.

In accordance with the provisions of the patent statutes, I havedescribed my invention, but I desire it understood that the process isnot confined to the particular steps or their sequence, exactly asdescribed, the same being merely illustrative, and that the inventionmay be carried out in a modified manner without departing from thespirit or leading principles of my inventive concept, and I also claimbroadly the right to employ all chemical equivalents, orinstrumentalities coming within the scope of the appended claims, and bymeans of which the enumerated objects of my invention are attained andnovel results accomplished, as it is obvious that the particular meansherein described, chemicals or quantities listed are only some of manythat can be employed according to the same principles an to obtain thesame objects and results.

Having now described my invention, what I claim and desire to secure byLetters Patent is: 1. A process or converting a mineral oil into anoxidizable oil, characterized by the following steps: heating saidmineral oil to a temperature not substantially above 100 0.,incorporating in it approximately up to one-fifth of its quantity of a.vegetable oil, containing fatty oxidizable acids, blowing a current, ofozone through the mixture of nitric acid, diluted in twice its weight ofalcohol to the ozonized compound, said diluted acid mixture to bebetween. one third to onehalf of the mineral and vegetable oil quantitycombined. 7

2. A process of converting a mineral oil into an oxidizable oil,characterized by the following steps: heating said mineral oil to atemperature not substantially abovelOO" (3., incorporating in itapproximately uprto one-fifth of its quantity of a vegetable oil,containing fatty oxidizable acids, together with a suitable dosage of anoxygenating catalyst, previously admixed, such as lead resinate, cobaltresinate and/or manganese resinate, blowing a current of ozone throughthe compound for about one hour, While maintaining a temperature ofabout 100 C., and adding a mixture of nitric acid, diluted in twice its

